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Origin of the Failure of Density Functional Theories in Predicting Inverted Singlet–Triplet Gaps
[Image: see text] Recent experimental and theoretical studies have shown several new organic molecules that violate Hund’s rule and have the first singlet excited state lower in energy than the first triplet excited state. While many correlated single reference wave function methods have successfull...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8900124/ https://www.ncbi.nlm.nih.gov/pubmed/35147428 http://dx.doi.org/10.1021/acs.jpca.1c10492 |
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author | Ghosh, Soumen Bhattacharyya, Kalishankar |
author_facet | Ghosh, Soumen Bhattacharyya, Kalishankar |
author_sort | Ghosh, Soumen |
collection | PubMed |
description | [Image: see text] Recent experimental and theoretical studies have shown several new organic molecules that violate Hund’s rule and have the first singlet excited state lower in energy than the first triplet excited state. While many correlated single reference wave function methods have successfully predicted excited-state energetics of these low-lying states, conventional linear-response time-dependent density functional theory (TDDFT) fails to predict the correct excited-state energy ordering. In this article, we have explored the performance of combined DFT and wave function methods like doubles-corrected TDDFT and multiconfiguration pair-density functional theory for the calculation of inverted singlet–triplet gaps. We have also tested the performance of the excited-state DFT (eDFT) method for this problem. Our results have shown that it is possible to obtain inverted singlet–triplet gaps both by using doubles-corrected TDDFT with a proper choice of double-hybrid functionals or by using eDFT. |
format | Online Article Text |
id | pubmed-8900124 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-89001242022-03-08 Origin of the Failure of Density Functional Theories in Predicting Inverted Singlet–Triplet Gaps Ghosh, Soumen Bhattacharyya, Kalishankar J Phys Chem A [Image: see text] Recent experimental and theoretical studies have shown several new organic molecules that violate Hund’s rule and have the first singlet excited state lower in energy than the first triplet excited state. While many correlated single reference wave function methods have successfully predicted excited-state energetics of these low-lying states, conventional linear-response time-dependent density functional theory (TDDFT) fails to predict the correct excited-state energy ordering. In this article, we have explored the performance of combined DFT and wave function methods like doubles-corrected TDDFT and multiconfiguration pair-density functional theory for the calculation of inverted singlet–triplet gaps. We have also tested the performance of the excited-state DFT (eDFT) method for this problem. Our results have shown that it is possible to obtain inverted singlet–triplet gaps both by using doubles-corrected TDDFT with a proper choice of double-hybrid functionals or by using eDFT. American Chemical Society 2022-02-11 2022-03-03 /pmc/articles/PMC8900124/ /pubmed/35147428 http://dx.doi.org/10.1021/acs.jpca.1c10492 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Ghosh, Soumen Bhattacharyya, Kalishankar Origin of the Failure of Density Functional Theories in Predicting Inverted Singlet–Triplet Gaps |
title | Origin of the Failure of Density Functional Theories
in Predicting Inverted Singlet–Triplet Gaps |
title_full | Origin of the Failure of Density Functional Theories
in Predicting Inverted Singlet–Triplet Gaps |
title_fullStr | Origin of the Failure of Density Functional Theories
in Predicting Inverted Singlet–Triplet Gaps |
title_full_unstemmed | Origin of the Failure of Density Functional Theories
in Predicting Inverted Singlet–Triplet Gaps |
title_short | Origin of the Failure of Density Functional Theories
in Predicting Inverted Singlet–Triplet Gaps |
title_sort | origin of the failure of density functional theories
in predicting inverted singlet–triplet gaps |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8900124/ https://www.ncbi.nlm.nih.gov/pubmed/35147428 http://dx.doi.org/10.1021/acs.jpca.1c10492 |
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